Manufacture of catalysts



typical equation:

chlorides, ketones can be prepared the following typical equation:

Patented Jam 27, 1942 UNITED :STATE s PATENT "OFFICE 2,211,299] MANUFACTURE orfoA'rALYs'rs Vladimir Ipatieif and Herman Pines, Chicago, 111., assignors to Universal Oil Products Company, Chicago, Ill., a corporation of Delaware No Drawing.

Application July 12, 1939,

Serial No. 283,996 I 13 Claims. 031. 252-251 a with the lmanufactureoi composite catalysts in which a'catalytically active heavy metal salt, together with a relatively inactive metal salt, is incorporated into a porous granular and adsorptive carrier so that the active ingredient is in eflect diluted and so that the particles produced resist disintegration and agglomeration in various types of vapor, liquid, and mixed phase catalytic operations involving organic compounds.

In one specific embodiment th present invention comprises the manufacture of catalysts for use in organic reactions by impregnating relatively inert granular materials with substantially anhydrous aluminum chloride and a rela tively inactive metal'halide.

The use of aluminumchloride in organic reactions, and particularly in reactions involving the various groups of hydrocarbons is well known in the art. For the sake of indicating certain types of reactions in which the present prepared catalyst can be employed the following brief summary is givenof some typical reactions in which aluminum chloride is employed as a catalyst or condensing agent: n.

l. Aromatic hydrocarbons can be with allryl halides according to 'the following CeHe CHaCl CsHaCBa '-l- HO] A101; Benzene methyl toluene chloride alklyated 2. In a development of'the above reactions an aryl-subetituted alkyl halide may be employedas typified by following equation:

according 3. Using 4. The use of aluminum chloride pos- {ecetophenouo hydrogen chloride according to the following simple equation:

0.35.011; BC] 00 CBH H0] AlCli CHO Toluoi tolylaidehyde 5. Organic acids can be prepared from aro- -matic hydrocarbons by the action of carbonyl chloride upon the aromatic hydrocarbon as shown below:

CI e C001: 0 CaHsC'OCl --v CIHICOOH Beam 1 cblori e 7 By the development of more complicated reactions corresponding in general tothose given in Sections 1 and 2, an extensive series of reacbenzoic acid tions is made possible whereby various types of hydrocarbons may be made to condense and form higher molecular weight products through reactions involving generally a primary halogenation followed by splitting off of the halogen -acid and the combination of, the resultant radicals. Aluminumchloride is used both as a cattalyst in thethermai conversion of relatively heavy petroleum hydrocarbon fractions to produce low boiling gasoline distillates, and also under more moderate conditions of treatment for the purification of these dis'tillates by causing the polymerization of .the more reactive oleflnic constituents. In the case or complicated hydrocarbonoil mixtures, such as the various fractions produced in the distillation and cracking of petroleum andother hydrocarbon oils it is to follow' the course ofthe various reac tione which-take place when aluminum chloride is employed; However, may. be grouped generallfunder the terms polymerization alkyla- .tion, and Aluminum chloride is also serviceable in eilecting isomerization tions. such-B for example, the of hexameth'ylene to methylcyclopent'ane, of normal parainn. into forms. a

nu within theecope of the a complex catalyst of' aluminum chlorides metal halide supported on a relatively inert ionn more easily and practically in a continuous operation.

Aluminum chloride, in some instances, is too I active as a catalyst to be used in chemical reactions. For instance, in the isomerization of npentane to iso-pentane the former undergoes, in many cases, undesirabledecomposition when the reaction is catalyzed by means of aluminum chloride-hydrogen chloride catalysts. Whenever aluminum chloride is used, the experimental m conditions have to be rigorously'controlled.

As one feature of the present invention it is proposed to decrease the violent activity of aluminum. chloride by diluting it with a metal halide which in itself has little or no catalytic ac- |5 tivity, the amount of the metal halide in proportion to the aluminum chloride depending upon the type of reaction which it is intended to carry out and the activity desired. Among the metal halides suitable for use in the present instance are included the halides of group 1 to 6 Y inclusive and group 8 of the periodic table in addition to the ammonium halides, the one chosen for a catalyst for a particular reaction depending upon the type of reaction and the temperatures employed. As 'a further feature of the invention, the aluminum chloride and metal halide are dispersed on a relatively inert granular ad-, sorbent prepared in such manner that the greatest possible surface is exposed to the reaction mixture.

In effecting various reactions among organic compounds utilizing aluminum chloride as a catalyst, difliculty is frequently encountered in that intermediate addition compounds are formed which are more or less of a sticky and viscous character, so that the original granules of anhydrous chloride become coated and the effective catalytic surface is lost. The tendency may be overcome to some extent by employing vigorous 4n agitation during the course of the catalytic reactions, but it can never be entirely obviated, so that in general the full eil'ectiveness of the aluminum chloride is never attained. The yields of reaction products are of such an order that to make operationsprofitable, the aluminum chloride must be recovered for reuse.

According to the present'invention, the above disadvantages'are to a large extent overcome by the use of composite granular catalysts, consisting in general of substantially inert porous adsorptive materials impregnated with substantially anhydrous aluminum chloride and a relatively inactive metal halide. Inert granular materials which may be used alternatively but obraw and acid treated, diatomaceous and infusorial 60 earth s, granular .pumice, and crushed porous porcelain.- In fact, practically any material which is' substantially unreactive with the aluminum chloride and other halides so that the desired stable properties of the catalyst granules are assured, may be employed. Of the supports mentioned, activated carbons, diatomaceous earths, and pumice are particularlyserviceable. Another property of anhydrous aluminum chloride which must be taken into account is its tendency to sublime at a temperature of approximately C. under atmospheric pressures, so that if it is employed at temperatures above. this point it must be injected or sublimed into the 7s reaction zone or the reactions must be carried out under pressure.

In the process of the present invention in which the aluminum chloride-metal halide complex is strongly absorbed by granular adsorbents, the disadvantages enumerated are to a large extent overcome as will be shown in the following paragraphs descriptive of the invention, .since the tendency of the aluminum chloride tobe too active to form a sludge, from which the aluminum chloride must be recovered and to volatilize is counteracted by the fusion with the metal halide and the absorbent action of the granular adsorbents employed, and since these supports apparently act to absorb and retain some of the viscous addition compounds and prevent the composite catalyst granules from adhering to form large agglomerates. Furthermore, the active catalyst on the adsorbent presents a greater surface area to the reaction, hence increasing the yields of reaction products over a given period of time.

Another reason for the use of certain metal halides as diluents for aluminum chloride is because in some instances they form mixtures with the aluminum chloride, the melting points of which mixtures, if the proportions are properly chosen, being below the temperature at which aluminum chloride sublimes and below the meltingpoints of the given metal halides. To illustrate this point, the following tabulation is given showing the melting points of mixtures of metal halides with aluminum chloride in given proportions:

- Melting point, C. (a) 6 parts anhydrous A1013, '3 parts NaCl,

and 1 part anhydrous FeCh 50- (b) MgClz+AlC13, containing 15.4 11101 MgClz g 186 (c) LiCl+A1Ch containing 41'mol men- 124 (d) KCl-i-AlCla containing 34.5 mol KCL- 158 We have found that the above described catalyst composites may be formed by two alternative methods, as .follows:

(1) The unactivemetal halide may be first added to the adsorbent and the aluminum chloride then added. In this case the adsorbent is saturated with an aqueous solution of the metal halide, dried, and then contacted with aluminum chloride under pressure at a temperature of about 300 C. The adsorbent being porous the metal halide is evenly distributed, and the aluminum chloride immediately forms a lowmeltingfused mixture with the metal halide and becomes dispersed in a controllably diluted form through the adsorbent. i

(2) Aluminum chloride and metal halide in predetermined proper proportions are mixed and heated at variedv temperatures under necessary 6 pressures, the conditions depending upon the metal halide used and the ratio of metal halide to aluminum chloride, and the fused mixture formed is contacted with the adsorbent. A uniformly distributed catalyst of aluminum' chloride-metal halide'supported on the adsorbent is obtained.

Upon examination, the product obtained by either of the above methods of preparation is dry and granular, the aluminum chloride metal;

halide apparently having disappeared, though it is actually present in the pores and on the sur-' face of the adsorbent as evidenced by the violent reaction of the granules with water and. the

catalytic activity in organic reactions.

The invention also comprises the manufacture color. It'was ioundto be applicabl a.

actions with substantially no tendency for the original particles to run together due to the formation of intermediatesludge-like products, so that much larger quantities of material may be treated before the catalyst has lost its activity.

Because the adsorbed aluminum chloride remains -in place without volatlllzation at considerably higher temperatures than its normal sublimation point. when vapors of reacting compounds are passed over a stationary granular bed of catalyst, the above described catalysts may be used in the vapor phase treatment of gasoline boiling range cracked distiliates for their relining, either as they are produced at the cracking plant or from rerun stills.

chloride.

The term "activated carbon" as used in the from granular carbonaceous materials such as 'wood char, and various varieties of coke by min- -eral acids and by the controlled heating, preferably under vacuum, to expel adsorbed liquids and gases. It is recognized that the various forms of active granular ch'ars will varyfconsiderably in adsorptive capacity so that therefore the properties of catalysts prepared in accordance with the present invention will varyboth in respect to the amount of metal halide and aluminum chloride which they are able to absorb and in respect-to the periods of service in which they are able to maintain a practical activity in different organic reactions. 7 It is within the scope of the invention and fre-' quentl preferable to utilize the composite consisting of aluminum chloride and a relatively inactive metal halide on inert porous adsorbents as formed particles such as may be made by pilling machines, using any type of substantially unreactive binder to produce structural strength in the pills. I

The following example is given to illustrate the present method of manufacturing catalysts for use in various organic reactions without any intent of unduly circumscribing the proper scope of the invention.

24' parts by weight of granular activated carv bon was added to a solution in water of 73 parts by weight of sodium chloride, the mixture being evaporated to dryness on a steam bath. .After this treatment the apparently dry product was further heated to a temperature of 350 C. to"

drive of! further amounts of adsorbed water. parts by weight of the activated carbon contain-' ing the adsorbed sodium chloride was placed in a various types of reactions among hydrocarbons. particularly the conversion of normally gaseous oleflns into-gasoline boiling range materials, the isomerization of normally liquid paraflin hydrocarbons into their corresponding isomeric-modincations and various types of alkylati'on" reactions involving the addition of alkyl groups toaromatics, parafnns, and naphthenes.

. We claim as our invention: 1

i. A process for producing catalysts which comprises adding to a solid adsorbent an aqueous solution of a catalytically inactivemetal halide. drying the resultant mixture, and then impregnating the mixture with an anhydrous aluminum halide.

2. A process for producing catalysts which comprises adding to a solid adsorbent an aqueous solution of a catalytically inactive metal halide, drying the resultant mixture, and then impregnating the mixture with anhydrous aluminum 3. A process for producing catalysts which 1 comprises adding'to a solid adsorbent an aqueous solution of an alkalinous metal halide, drying the resultant mixture, and then impregnating the mixture with an anhydrous aluminum halide.

4. A process for producing catalysts which comprises'adding to a solid adsorbent an alqueous solution of sodium chloride, drying the-resultant mixture, and then impregnating the mixture with anhydrousaluminum chloride.

5. A process for producing catalysts which comprises adding to a solid adsorbent an aqueous solution of a catalytically inactive metal halide, drying the resultant mixture, and then impregnating the mixture with anhydrous aluminum chloride at a temperature above the normal sublimation point of aluminum chloride and under superatmospheric pressure.

6. A process for producing catalysts which comprises adding to a solid adsorbent an aqueous solution of a catalytically inactive metal halide, drying the resultant mixture, and then impregnating the mixtur with anhydrous aluminum chloride at about 300 C. and under superatmospheric pressure.

7. A process for producing catalysts which comprises adding toa solid adsorbent an aqueous solution of a catalytically inactive metal halide, drying the resultant mixture, and then impregnating the mixture with an anhydrous aluminum halide under temperature and pressure conditions adequate to fuse thealuminum halide with said inactive metal halide.

8. A process for I producing catalysts which comprises adding to a solid adsorbent an aqueous solution of a catalytically inactive metal halide, drying the, resulting mixture, and then impregnating the mixture with anhydrous aluminum chloride under temperature and pressure conditions adequate to fuse the aluminum chloride with said inactive metal halide.

pressure vessel containing 40 parts by weight of finely divided granular substantially anhydrous aluminum chloride. An equivalent of 9 parts by weight of hydrogen chloride was introduced under pressure and the contents of the vessel were heated for three hours, at 300 C. under a hydrogen pressure of approximately 35 atmospheres.

The granular material recovered from the pressure. vessel wasapparently vdryand had a 1 9. A process for the manufacture of composite granular materials applicable to catalyzing organic reactions which comprises saturating a granular adsorbent with an aqueous solution of a metal halide of relatively low activity selected from the group consisting of the halides of the alkali and alkaline earth metals, drying the mix- 0 ture, and subsequently adding anhydrousaluminum chloride to said mixture.

, 10. A process for the manufacture ofcomposite granular materials applicable to catalysing organic reactions which comprises saturating granular activated carbon with an aqueous solution 01' a metal halide or relatively low activity selected from the group consisting of the halides oi the alkali and alkaline earth metals, drying the mixture, and subsequently adding anhydrous aluminum chloride to said mixture under superatmospheric pressure sumcient to prevent-substantial sublimation or said aluminum chloride. A

' 11. A process for the manufacture of composite granular materials applicable to catalyzing organic reactions which comprises saturating granular activated carbon with an aqueous solution of a metal halide or relatively low activity selected from the group consisting of the halides of the alkali and alkaline earth metals, drying the mixture, and subsequently adding anhydrous aluminum "chloride to said mixture at a temperature of the order of 300 C. under superatmospheric pressure sufllcient to prevent substantial sublimation of said aluminum chloride. 12. A process i'orthe manufacture of composite granular materials applicable to catalyzing organic reactions which comprises saturating a granular adsorbent with an aqueous solution of a metal halide of relatively low activity selected from the group consisting of the halides of the alkali and alkaline earth metals, drying the mixture, and subsequently adding anhydrous alumia metal halide of relatively low activity selected from the group consisting of the halides oi the alkali and alkaline earth metals, drying the mixture, and subsequently adding anhydrous aluminum chloride to said mixture at a temperature of the order of 300 C. under a super-atmospheric pressure sufllcient to prevent substantial subli- -mation of said aluminum chloride.

VLADIMIR IPATIEFF. HERMAN PINES. 

